Manufacturing method of a semiconductor device, and substrate processing apparatus

ABSTRACT

An object of this invention is to make it possible to suppress early-stage oxidation of a substrate surface prior to oxidation processing, and to remove a natural oxidation film. For this reason, a method is provided comprising the steps of loading a substrate into a processing chamber, supplying a hydrogen-containing gas and an oxygen-containing gas into the processing chamber, and subjecting a surface of the substrate to oxidation processing, and unloading the substrate subjected to oxidation processing from the processing chamber. In the oxidation processing step, the hydrogen-containing gas is introduced in advance into the processing chamber, with the pressure inside the processing chamber set at a pressure that is less than atmospheric pressure, and the oxygen-containing gas is then introduced in the state in which the introduction of the hydrogen-containing gas is continued.

This is a Division of application Ser. No. 11/885,869 filed Oct. 29,2007, which in turn is a National Phase of Application No.PCT/JP2006/304429 filed Mar. 8, 2006. The disclosure of the priorapplications is hereby incorporated by reference herein in its entirety.

BACKGROUND

The present invention relates to a manufacturing method of asemiconductor device and to a substrate processing apparatus for theoxidation processing of a substrate surface.

As the degree of integration of semiconductor devices has increased, anincrease in wiring resistance has become a problem. The materials ofgate electrodes primarily used in memory processes have shifted fromconventional polysilicon doped with impurities to silicide films thatmake it possible to lower the resistance value and polymetal structuresin which metal materials such as tungsten and the like are stacked ontop of polysilicon. Here, silicide films (also referred to as silicatefilms) are films that are formed by the fusion of metals and silicon.Polymetal structures are structures in which metals are stacked on topof polysilicon, and are structures in which a barrier metal is insertedbetween the polysilicon and metal in order to prevent silicateformation.

The polymetal structures and silicide films mentioned above will bedescribed using as an example the gate electrodes shown in FIG. 4 g.These electrodes are parts of a flash memory or DRAM. Furthermore, FIGS.4( a) and 4(c) show portions of the structures of flash memories, andFIG. 4( b) shows a portion of the structure of a DRAM.

FIG. 4( a) shows one example in which a polymetal structure is appliedto the gate electrode (control electrode) of a flash memory. In order toform a polymetal structure, a surface of a silicon substrate 100constituting a dynamic layer is thermally oxidized, and a silicondioxide film (SiO₂ film) 110 used for gate insulation is formed; apolysilicon film (poly-Si film) 120 used as a floating gate is depositedon top of this SiO₂ film. A poly-Si film 140 used as a gate electrode isstacked on top of this poly-Si film 120, with an SiO₂/Si₃N₄/SiO₂ film(insulating film having an ONO structure) 130 or the like interposed asan insulating film. In order to lower the resistance, a tungsten nitride(WN) film 150 is formed as a barrier metal, and a tungsten (W) film 160is deposited as a metallic thin film on top of this. Subsequently, thestacked films described above are patterned by a dry etching method, sothat a structure having a polymetal gate 200 having a stacked structureis formed on the gate region between the source region 80 and drainregion 90 as shown in FIG. 4( a).

FIG. 4( b) shows one example in which a polymetal structure is appliedto the gate electrode of a DRAM. This example differs from FIG. 4( a) inthat there is no poly-Si film 120 or insulating film 130 having an ONOstructure; the remaining structure is the same. Furthermore, FIG. 4( c)shows an example in which a silicide film, e.g., a tungsten silicide(WSi) film 170, is used instead of the polymetal structure in FIG. 4(a). This example differs from FIG. 4( a) in that a WSi film 170 isdeposited on top of the poly-Si film 140 formed on a surface of theinsulating film 130 having an ONO structure.

The dry etching method used to pattern stacked films is a workingoperation in which a surface of the stacked films is physically shavedoff by sputtering. In the polymetal gate structure shown in FIG. 4( a)as an example, damage is inflicted on the surface of the siliconsubstrate 100 in the source region 80, drain region 90, and the like,and on the side surfaces of the thermal oxidation film (SiO₂ film) 110,poly-Si film 120, insulating film 130 having an ONO structure, poly-Sifilm 140, and the like, and this leads to an increase in the wiringresistance and an increase in the leak current.

In cases in which impurity-doped polysilicon is used as the material ofthe gate electrode, in order to recover from this damage inflicted onthe surface of the silicon substrate 100 and side surfaces of thethermal oxidation film and the like by dry etching, and in order to forma protective film, the moisture generated on the outside of theprocessing chamber is usually supplied to the interior of the processingchamber at normal pressure or under reduced pressure, and a thermaloxidation film used for protection is formed on the surface of thesilicon substrate 100 and the side surfaces of the thermal oxidationfilm and the like by this moisture (for example, see patent document 1).

Patent document 1: Japanese Laid-Open Patent Application No. 2002-110667

SUMMARY

However, when a silicide film or polymetal structure is used as the gateelectrode, supplying moisture to the processing chamber causes thesilicide film constituting the outermost surface or the surface of themetal material used in the polymetal to be easily oxidized in the samemanner by this moisture during the formation of the thermal oxidationfilm used for protection, and the problem of an increase in the wiringresistance is encountered.

Furthermore, there are also methods in which oxidation is accomplishedby introducing a hydrogen-containing gas and an oxygen-containing gasdirectly into the processing chamber under reduced pressure rather thanintroducing moisture into the processing chamber. However, in suchconventional methods, an oxygen-containing gas is supplied in advance ofa hydrogen-containing gas, or an oxygen-containing gas is suppliedsimultaneously with a hydrogen-containing gas, basically in order tosuppress surface roughness caused by the thermal etching of the siliconsubstrate. Accordingly, there is a danger that the silicide film ormetal thin film on a surface of the substrate will be oxidized not onlyduring the oxidation processing but also prior to the oxidationprocessing.

It is an object of the present invention to provide a manufacturingmethod of a semiconductor device and a substrate processing apparatus inwhich early-stage oxidation of the substrate surface prior to theoxidation processing can be suppressed, and in which only the siliconsubstrate surface and layers containing silicon atoms and not containingmetal atoms, such as a thermal oxidation film and the like, can beselectively oxidized without oxidizing layers containing metal atomssuch as silicide film, metal materials, and the like.

In one aspect of the present invention, a manufacturing method of asemiconductor device is provided comprising the steps of loading asubstrate into a processing chamber, supplying an oxygen-containing gasand a hydrogen-containing gas into the processing chamber and subjectinga surface of the substrate to oxidation processing, and unloading thesubstrate from the processing chamber following the oxidationprocessing, wherein, in the oxidation processing step, thehydrogen-containing gas is introduced in advance into the processingchamber, with the pressure inside the processing chamber set at apressure that is less than atmospheric pressure, and theoxygen-containing gas is then introduced in the state in which theintroduction of the hydrogen-containing gas is continued.

In another aspect of the present invention, a manufacturing method of asemiconductor device is provided comprising the steps of loading asubstrate in which at least a layer that contains silicon atoms but doesnot contain metal atoms and a layer that contains metal atoms areexposed at the surface into a processing chamber, supplying anoxygen-containing gas and a hydrogen-containing gas into the processingchamber and subjecting a surface of the substrate to oxidationprocessing, and unloading the substrate from the processing chamberfollowing the oxidation processing, wherein, in the oxidation processingstep, the pressure inside the processing chamber is set at a pressurethat is less than atmospheric pressure, and the flow rate ratio B/A ofthe flow rate B of the hydrogen-containing gas to the flow rate A of theoxygen-containing gas is set at 2 or greater.

In the first aspect of the present invention, a hydrogen-containing gasis introduced in advance of an oxygen-containing gas; accordingly,initial-stage oxidation of the substrate surface prior to the regularoxidation can be suppressed, and the natural oxidation film on thesurface of the substrate can be removed.

Furthermore, in cases in which at least a layer that contains siliconatoms but does not contain metal atoms and a layer that contains metalatoms are exposed at the surface of the substrate in accordance with theother aspect of the present invention, only the layer that containssilicon atoms but does not contain metal atoms can be selectivelyoxidized without oxidizing the layer that contains metal atoms.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a process sequence diagram showing one example of theoxidation processing according to an embodiment;

FIG. 2 is a comparative diagram of film thickness data for oxidationfilms obtained in a case in which such oxidation films were formed onsilicon substrates using the oxidation processing methods of theembodiment and a comparative example;

FIG. 3 is an explanatory diagram showing the construction of a verticalsemiconductor manufacturing apparatus used as substrate processingapparatus according to the embodiment;

FIG. 4 is a laminated structure diagram illustrating various types ofgates of semiconductor devices;

FIG. 5 is an explanatory diagram showing the effect of hydrogen-richconditions according to the embodiment;

FIG. 6 is a diagram showing pressure fluctuations inside the furnace ina case in which H₂ and O₂ were supplied to the furnace with the H₂/O₂flow rate ratio varied;

FIG. 7 is a diagram showing the results obtained when a judgment wasmade as to whether or not isotropy was maintained in a case in whichoxidation films were formed on silicon substrates with the pressureinside the furnace varied; and

FIG. 8 is a diagram showing the results obtained when a judgment wasmade as to whether or not selective oxidation could be achieved in acase in which tungsten and silicon were processed with the H₂/O₂ flowrate ratio varied.

DETAILED DESCRIPTION OF EMBODIMENTS

The present inventors discovered that even if the hydrogen-containinggas is introduced into the processing chamber in advance of theoxygen-containing gas, no localized volume expansion occurs in theprocessing chamber as long as the interior of the processing chamber isplaced under a reduced pressure. Furthermore, the present inventorsdiscovered that the oxidation reaction of the silicide film or metalmaterial (layer that contains metal atoms) exposed at the surface can besuppressed by placing the interior of the processing chamber under areduced pressure and introducing the hydrogen-containing gas in advanceof the oxygen-containing gas into the processing chamber after thesubstrate is loaded into the processing chamber. Moreover, the presentinventor discovered that the natural oxidation film that is formed on asurface of the substrate can also be removed in this case. In addition,the present inventor discovered conditions under which the recovery fromdamage to the surface of the silicon substrate And to the side surfacesof the thermal oxidation film and the like (layer that contains siliconatoms but does not contain metal atoms) exposed by dry etching can beaccomplished, and a thermal oxidation film that protects these layerscan be formed, while maintaining reducibility with respect to thesilicide film and metal material, by adding a small amount of anoxygen-containing gas to the processing chamber kept at a reducedpressure and provided with a reducing atmosphere created by ahydrogen-containing gas. The present invention is based on thesefindings, which have been discovered by the present inventors.

Embodiments of the present invention will be described below withreference to the attached figures.

FIG. 3 shows a batch type vertical semiconductor manufacturing apparatus(oxidation apparatus) as one example of the construction of a substrateprocessing apparatus used to work the present invention.

The reaction furnace 20 has a reaction tube 21 made of quartz. A boat 2used as a substrate holder is inserted into the processing chamber 4(hereafter also referred to simply as a furnace) formed by this reactiontube 21. The boat 2 is constructed so as to hold a plurality of siliconwafers 1 in a plurality of stages at intervals (substrate pitchintervals) in a substantially horizontal state. The bottom of thereaction tube 21 is open in order to allow insertion of the boat 2; thisopen part can be tightly closed by a sealing cap 22. The boat 2 iscarried on a heat insulating cap 25, and the heat insulating cap 25 isattached to the rotating mechanism 27 via a rotating shaft 26. Aresistance-heating heater 5 is disposed around the reaction tube 21 as aheating source. Connected to the reaction tube 21 are an oxygen supplyline 7 used as an oxygen-containing gas supply line that supplies oxygen(O₂) gas as an oxygen-containing gas to the silicon wafers 1 from theupstream side of the disposition region of the silicon wafers 1, and ahydrogen supply line 8 used as a hydrogen-containing gas supply linethat supplies hydrogen (H₂) gas as a hydrogen-containing gas to thesilicon wafers 1 from the upstream side of the disposition region of thesilicon wafers 1.

The oxygen supply line 7 is connected to an oxygen gas supply source 41,and the hydrogen supply line 8 is connected to a hydrogen gas supplysource 42. The oxygen supply line 7 and hydrogen supply line 8 aredisposed so that these lines pass through the ceiling wall 31 of thereaction tube 21. The gas jetting openings of the oxygen supply line 7and hydrogen supply line 8 that pass through in this way are orienteddownward, and are arranged so that oxygen gas and hydrogen gas are eachcaused to jet downward.

The supply lines 7 and 8 are provided with electromagnetic valves 6 aand 6 b which are used to supply the gases and stop the supply of thegases, and mass flow controllers (flow rate control devices) 12 a and 12b which allow the adjustment of the flow rates of the respective gases.Furthermore, an exhaust line 23 which discharges the processing gases isconnected to the reaction tube 21, a vacuum pump 3 is connected to thisexhaust line 23, and the apparatus has a structure that maintains theinterior of the reaction tube 21 at a specified pressure. Duringsubstrate processing, the interior of the reaction tube 21 is maintainedby the vacuum pump 3 at a specified pressure that is lower thanatmospheric pressure (reduced pressure); this pressure control isaccomplished by a controller 24 used as a control means.

The controller 24 also controls the operation of a rotating mechanism27, the electromagnetic valves 6 a and 6 b, the mass flow controllers 12a and 12 b, and other units that constitute the oxidation apparatus.

Next, a method for performing oxidation processing on a surface of asubstrate As one step of a semiconductor device manufacturing processusing the oxidation apparatus described above will be described withreference to FIGS. 1 and 3.

FIG. 1 shows one example of the process sequence of the oxidationprocessing in the present invention. Furthermore, in the followingdescription, the operation of the respective parts constituting theoxidation apparatus is controlled by the controller 24.

One batch of silicon wafers 1 is transferred to the boat 2. The interiorof the reaction furnace 20 is heated to a specified temperature(substrate loading temperature), e.g., a specified temperature in therange of 300 to 600° C., and this state is maintained. The plurality ofsilicon wafers 1 placed into the boat 2 are loaded into the processingchamber 4 of the reaction furnace 20 whose heated state is maintained,and the interior of the reaction tube 21 is tightly closed by thesealing cap 22 (substrate loading step). Here, at least a layer whichcontains silicon atoms but does not contain metal atoms and a layerwhich contains metal atoms are exposed at a surface of the siliconwafers 1 loaded in the boat 2. A silicon single crystal substrate,poly-Si film, Si₃N₄ film, or SiO₂ film may be used as the layer whichcontains silicon atoms but does not contain metal atoms. Furthermore, asilicide film, metal film, or metal oxide film may be used as the layerwhich contains metal atoms.

The interior of the processing chamber 4 into which the silicon wafers 1have been loaded is evacuated by the vacuum pump 3, and the pressureinside the furnace is controlled by the controller 24 to a specifiedpressure that is lower than atmospheric pressure (101.3 kPa) (reactionchamber pressure reduction step). This specified pressure is thepressure inside the processing chamber 4 (advance introduction pressureP) when the hydrogen gas is introduced in advance, as will be describedlater, and is greater than the oxidation processing pressure Q that willbe described later. Furthermore, the boat 2 is caused to rotate at aspecified rotational speed by the rotating mechanism 27.

After the pressure inside the processing chamber 4 has been reduced tothe advance introduction pressure P, hydrogen gas is directly introducedinto the processing chamber 4 in advance of the oxygen gas (advanceintroduction of hydrogen) from the hydrogen supply line 8 prior to thetemperature increase step described later. Subsequently, the flow ofhydrogen gas is continued (hydrogen-containing gas flow step) up to apoint prior to the atmospheric pressure leak step described later. Theintroduction of hydrogen gas is performed from a point prior to the stepof increasing the temperature inside the processing chamber 4; however,it is sufficient if the introduction of hydrogen gas is performed atleast from the step of increasing the temperature inside the processingchamber 4.

In the state in which the supply of hydrogen gas is continued, thetemperature inside the processing chamber 4 is increased from thesubstrate loading temperature, which is the temperature maintained atthe time that the silicon wafers are loaded, to the oxidation processingtemperature (temperature increase step). A specified temperature in therange of 800 to 900° C. may be indicated as an example of the oxidationprocessing temperature.

Following the temperature increase, the temperature of the processingchamber 4 as a whole is controlled by the controller 24 so that thistemperature is stably maintained at the specified oxidation processingtemperature (temperature stabilization step).

When the temperature of the processing chamber 4 as a whole has beenstabilized, or while the temperature of the processing chamber 4 as awhole is stabilized, the pressure inside the furnace is controlled bythe controller 24 so that this pressure is a specified oxidationprocessing pressure Q that is lower than the advance introductionpressure P. The oxidation processing pressure is set at 1333 Pa (10torr) or less.

Subsequently, in the state in which the introduction of hydrogen gas iscontinued, oxygen gas is directly introduced into the processing chamber4 from the oxygen supply line 7 (subsequent introduction of oxygen). Inthis case, the flow rate ratio B/A of the flow rate B of hydrogen gas tothe flow rate A of oxygen gas is set at 2 or greater.

As a result of the introduction of oxygen gas, oxygen gas and hydrogengas react in an atmosphere under a reduced pressure that is heated bythe resistance-heating heater 5, and reaction species such as ions andthe like are produced; oxidation of the silicon wafers 1 is caused toproceed by these reaction species. Oxidation processing is performed bycausing oxygen gas to flow for a specified time in the state in whichthe introduction of hydrogen gas is continued (oxidation processingstep). Furthermore, in the present invention, oxidation processing isperformed under hydrogen-rich conditions. Here, the term “hydrogen-rich”refers to a case in which B/A≧2, where A is the flow rate of oxygen gas,and B is the flow rate of hydrogen gas.

Subsequently, the introduction of oxygen gas is stopped in the state inwhich the introduction of hydrogen gas is continued, and the oxidationprocessing is ended. Specifically, the introduction of oxygen gas isperformed in a step in which the temperature inside the processingchamber is at least maintained at the oxidation processing temperatureas indicated by the arrow-symbol interval of the oxygen-containing gasflow shown in FIG. 1 (oxygen-containing gas flow step).

When the oxidation processing of the silicon wafers 1 is ended, theresidual gas inside the processing chamber 4 is removed via the exhaustline 23 by purging with an inert gas, vacuum evacuation by the vacuumpump 3, or the like (purging step), and the interior of the processingchamber 4 is set at a high degree of vacuum, e.g., a pressure of 0.01 Paor less. In the state in which the pressure inside the processingchamber 4 is maintained at a pressure of 0.01 Pa or less, thetemperature inside the furnace is lowered from the oxidation processingtemperature to a specified substrate loading temperature, e.g., aspecified temperature in the range of 300 to 600° C. (temperaturelowering step). Furthermore, during this period as well, hydrogen gas iscaused to flow continuously without any modification, and the supply ofhydrogen gas is stopped following the lowering of the temperature.Furthermore, the hydrogen gas may also be stopped at the oxidationprocessing temperature prior to the lowering of the temperature, afterthe oxidation processing is ended.

As is shown by the arrow-symbol interval of the hydrogen-containing gasflow shown in FIG. 1, the introduction of hydrogen gas is continued frombefore the step of increasing the temperature in the processing chamber4 until after the completion of the step of lowering the temperature inthe processing chamber 4. Alternatively, the introduction of hydrogengas may also be continued from at least the step of increasing thetemperature in the processing chamber 4 up to a point prior to thelowering of the temperature in the processing chamber 4, or until thestep of lowering the temperature is completed.

After the supply of hydrogen gas is stopped, the pressure inside theprocessing chamber 4 is returned to atmospheric pressure (101.3 kPa) bysupplying an inert gas such as N₂ or the like to the processing chamber4 (atmospheric pressure leak step). Subsequently, the boat 2 is unloadedfrom the processing chamber 4 of the reaction furnace 20, and thesilicon wafers 1 that have been subjected to oxidation processing areunloaded (substrate unloading step). The boat 2 is caused to wait in aspecified position until the cooling of all of the silicon wafers 1supported in the boat 2. When the silicon wafers 1 held in the boat 2that is caused to wait have cooled to a specified temperature, thesilicon wafers 1 are recovered by a substrate transfer mechanism or thelike.

In this way, the process sequence in oxidation under hydrogen-richconditions obtained by the advance introduction of hydrogen iscompleted.

Furthermore, a furnace temperature of 600 to 1100° C., preferably 800 to900° C., a furnace pressure of 13.3 to 1333 Pa (0.1 to 10 ton),preferably 13.3 to 133 Pa (0.1 to 1 ton), an H₂ flow rate of 0.5 to 5.0slm, preferably 1.0 to 2.0 slm, an O₂ flow rate of 0.05 to 2.0 slm,preferably 0.05 to 0.5 slm, and an H₂/O₂ flow rate ratio of 2 to 5,preferably 4 to 5, may be cited as an example of preferred processingconditions of the oxidation processing in the present embodiment.Oxidation processing is performed with the respective processingconditions maintained at specified values within these ranges.

In the present embodiment, oxidation is performed at 500° C. or greaterunder hydrogen-rich conditions with the advance introduction ofhydrogen; conventionally, however, oxidation has not been performedunder hydrogen-rich conditions with the advance introduction ofhydrogen.

The reason for this is that it was believed that if O₂ were to besubsequently introduced into a reaction system at atmospheric pressureand at a temperature of 500° C. or greater following the advanceintroduction of hydrogen, and the H₂O₂ flow rate ratio in this case wereset at 2.0 or greater (hydrogen-rich), a chain reaction would be inducedby the reaction heat, and this would be accompanied by localized volumeexpansion, thus entering the explosive range and rendering the processdangerous in a reaction system using a quartz vessel.

However, it was demonstrated that localized volume expansion duringprocessing can be prevented by placing the reaction system under areduced pressure. It is inferred that the reason for this is that inprocessing under a reduced pressure, a large exhaust rate is constantlyobtained by means of the vacuum pump in the reaction system, so thatpressure fluctuations giving rise to localized volume expansion areabsorbed. Furthermore, in particular, it was also demonstrated that theexplosive range can be avoided by reducing the pressure of the reactionsystem to 1333 Pa (10 torr) or less. The reason for this is that theprobability of collision between H₂ and O₂ in the reaction system isreduced by reducing the pressure of the reaction system to a value thatis equal to or less than the value described above, so that the quantityof heat generated by the heat of the reaction that is necessary in orderto reach a chain reaction is not supplied.

This will be described with reference to FIG. 6. FIG. 6 is a diagramshowing pressure fluctuations in the furnace in a case in which H₂ andO₂ are supplied to the furnace, with the H₂/O₂ flow rate ratio variedunder conditions which are such that the H₂/O₂ flow rate ratio is 2 orgreater (hydrogen-rich), in the state in which the interior of thefurnace is evacuated by the vacuum pump. The horizontal axis shows theH₂/O₂ flow rate (slm), and the vertical axis shows the pressure (Pa)inside the furnace. Furthermore, the H₂ flow rate was fixed at 1.0 slm,and only the O₂ flow rate was varied as follows: 0 slm, 0.1 slm, 0.2slm, 0.4 slm, 0.5 slm.

It is seen from FIG. 6 that when the temperature inside the furnace isset at 300° C., the pressure increases monotonically depending on the O₂flow rate. This indicates that no reaction is taking place in thefurnace. On the other hand, it is seen that when the temperature insidethe furnace is set at 600° C., almost no increase in pressure isobserved. This indicated that some type of reaction is taking place inthe furnace. Furthermore, in cases in which the temperature inside thefurnace is set at a temperature greater than 600° C., e.g., 800° C., itis likewise the case that almost no increase in pressure is observed.Moreover, it was demonstrated that no pressure fluctuation occurs in thefurnace, either when the pressure inside the furnace is set at 133 Pa (1torr), or when this pressure is set at 1333 Pa (10 ton). It is seen fromthese facts that if the pressure inside the furnace is set at 1333 Pa(10 torr) or less during the oxidation processing, no pressurefluctuation occurs inside the furnace, and there is no danger of anexplosion due to an increased-rate reaction.

Furthermore, it was also demonstrated that if the pressure inside thefurnace is set at 1333 Pa (10 ton) or less, isotropy is maintained withno dependency on plane orientation. This will be described withreference to FIG. 7. FIG. 7 shows the results obtained when it wasdetermined whether or not isotropy was maintained in a case in which anoxidation film was formed on silicon substrates having different crystalplane orientations (110), (100) while the temperature inside the furnacewas kept at 800 to 900° C., the H₂/O₂ flow rate ratio was kept at 2 orgreater, and the pressure inside the furnace was varied. Here,furthermore, isotropy is expressed by the ratio T1/T2 (hereafterreferred to as isotropy (110)/(100)) of the film thickness T1 of theoxidation film formed on a silicon substrate having a crystal planeorientation of (110) to the film thickness T2 of the oxidation filmformed on a silicon substrate having a crystal plane orientation of(100); in cases in which the isotropy (110)/(100)=1.00 to 1.10, it isjudged that isotropy is maintained, while in cases in which the isotropy(110)/(100)>1.10, it is judged that isotropy is not maintained. In FIG.7, O indicates that isotropy is maintained, and x indicates thatisotropy is not maintained.

It is seen from FIG. 7 that isotropy is maintained in cases in which thepressure inside the furnace is set at 1333 Pa (10 torr) or less, butthat isotropy is not maintained in cases in which the pressure insidethe furnace is set at 13330 Pa (100 ton) or greater. The reason for thisis thought to be as follows: namely, in cases in which the pressureinside the furnace is set at 1333 Pa (10 ton) or less, reaction speciessuch as ions and the like are generated by the reaction of H₂ and O₂inside the furnace, and these reaction species contribute to oxidation;however, in cases in which the pressure inside the furnace is set at13330 Pa (100 ton) or greater, such reaction species are not generated.It is seen from this as well that it is preferable to set the pressureinside the furnace at 1333 Pa (10 torr) or less.

The actions and effects of the present embodiment will be cited below in(A) through (E).

(A) In the present embodiment, since hydrogen gas is introduced inadvance of oxygen gas, the following actions and effects are obtained.

(1) Oxidation of the silicide film, metal films, and the like prior tothe oxidation processing can be prevented.

Advance introduction of oxygen, which is an oxidizing species, causedoxygen-induced oxidation to proceed. However, by preferentiallyintroducing hydrogen, it is possible to maintain the interior of theprocessing chamber 4 in an atmosphere of a reducing gas that contains nooxidizing species, and oxidation can be prevented.

(2) Early-stage oxidation of the silicon substrate, a surface of thepoly-Si film, and the like can be suppressed.

Advance introduction of oxygen, which is an oxidizing species, causedoxygen-induced oxidation to proceed. However, by preferentiallyintroducing hydrogen, it is possible to maintain the interior of theprocessing chamber 4 in an atmosphere of a reducing gas that contains nooxidizing species, and oxidation can be prevented.

(3) The naturally oxidized films on the silicon substrate, on a surfaceof the poly-Si film, and the like can be removed.

Advance introduction of oxygen, which is an oxidizing species, causedoxygen-induced oxidation to proceed. However, by preferentiallyintroducing hydrogen, it is possible to maintain the interior of theprocessing chamber 4 in an atmosphere of a reducing gas that contains nooxidizing species, and oxidation can be prevented. In addition, bysetting the pressure at a specified pressure (advance introductionpressure P), it is possible to remove natural oxidation films bysublimation.

(B) Furthermore, in the present embodiment, the advance introductionpressure P inside the processing chamber 4 when hydrogen gas isintroduced in advance is set at a larger value than the oxidationprocessing pressure Q that is maintained when oxygen gas is introducedin the state in which the introduction of hydrogen gas is continued.Accordingly, surface roughness caused by thermal etching can beprevented.

A problem that must be dealt with when a silicon surface is subjected tooxidation processing is the relationship between the oxidationprocessing temperature and the pressure inside the reaction tube 21. Incases in which the oxidation processing temperature is a hightemperature of 850° C. to 900° C., if a state is encountered in whichthe pressure inside the reaction tube 21 is as low as approximately 0.01Pa (high vacuum), there is a possibility that surface roughness of thesilicon known as thermal etching may arise. It is believed that thissurface roughness may cause dissociation of the silicon to occur in astate of high temperature and low oxygen partial pressure, and thiscauses the device characteristics to deteriorate.

Accordingly, thermal etching may be prevented by not reducing thepressure any more than necessary, and setting the pressure at a valuethat is a little higher than a high vacuum, in the state in which theinterior of the furnace is placed in a hydrogen atmosphere prior tooxidation processing. In the present embodiment, the value of theadvance introduction pressure P is set at a pressure that is higher thanthe pressure Q during oxidation processing, so that the advanceintroduction pressure P inside the reaction tube 21 will not be reducedto around 0.01 Pa in the vicinity of the temperature prior to oxidationprocessing. In cases in which the oxidation processing temperature isaround 850° C. or less, it is preferred that the value of the advanceintroduction pressure P be set at 133 to 13330 Pa; in cases in which theoxidation processing temperature is around 900° C. or less, it ispreferred that the value of the advance introduction pressure P be setat 6500 to 13330 Pa. It has also been demonstrated that there is asimilar tendency to prevent thermal etching in cases in which theinterior of the furnace is placed in an N₂ atmosphere.

Thus, although there are differences according to the oxidationprocessing temperature, roughness of the silicon surface caused bythermal etching that might conceivably occur during oxidation processingof the silicon surface can be effectively prevented by controlling thepressure inside the furnace so that this pressure is maintained at theadvance introduction pressure P which is considerably higher than theoxidation processing pressure Q prior to oxidation processing, ratherthan lowering this pressure all at once by vacuum evacuation fromatmospheric pressure (101.3 kPa) that is maintained at the time ofintroduction into the furnace to the oxidation processing pressure thatis maintained prior to the step of increasing the temperature inside theprocessing chamber 4.

(C) Furthermore, in the present embodiment, since the conditions usedwhen oxidation processing is performed are set as hydrogen-richconditions, the following actions and effects are obtained.

(1) Selective Oxidation

The oxidation of layers containing metal atoms such as the silicidefilm, metal films, and the like (hereafter also referred to simply asmetals) is prevented, and a thermal oxidation film can be selectivelyformed to protect layers that contain silicon atoms but do not containmetal atoms, such as the silicon substrate, a surface of the poly-Sifilm, and the like (hereafter also referred to simply as silicon).Specifically, in cases in which a very small amount of O₂ is added tothe H₂ of the reducing atmosphere, regions are obtained in which theselective oxidation of silicon and metals is possible.

In an atmosphere of O₂ alone, oxidation proceeds on both silicon andmetal surfaces in a manner that depends on temperature and pressure.Furthermore, in an atmosphere of H₂ alone, oxidizing species are notpresent at normal temperature and normal pressure; accordingly,oxidation of silicon and metal surfaces does not proceed. However, whenthe temperature is increased and the pressure is reduced in an H₂atmosphere, the natural oxidation film present on silicon and metalsurfaces undergoes sublimation. Oxidation and sublimation are phenomenathat are induced by the same energy; however, whether oxidation orsublimation proceeds is determined by the mixture ratio, i.e., flow rateratio, of the O₂ that forms the oxidizing atmosphere and H₂ that formsthe reducing atmosphere. The probability of a sublimation reactionoccurring increases as the flow rate ratio of H₂ to O₂ becomes larger.The energy required for the formation of an oxidation film or forsublimation differs in silicon and metals. Selectivity at which siliconis oxidized but metals are not oxidized can be obtained if the flow rateratio of O₂ and H₂ is varied and hydrogen-rich conditions are set, i.e.,if the flow rate ratio B/A of the H₂ flow rate B to the O₂ flow rate Ais set at 2 or greater.

In particular, if the pressure inside the processing chamber 4 is set at1333 Pa (10 ton) or less, preferably 133 Pa (1 ton) or less, and theflow rate ratio B/A is set at 2 or greater, preferably 4 or greater,only layers that contain silicon atoms but do not contain metal atomscan be selectively oxidized without oxidizing layers that contain metalatoms, especially tungsten.

This will be described with reference to FIG. 8. FIG. 8 shows theresults obtained when it was determined whether or not selectiveoxidation could be performed in a case in which tungsten was processedas a layer that contains metal atoms, and silicon was processed as alayer that contains silicon atoms but does not contain metal atoms whilethe temperature inside the furnace was kept at 800 to 900° C., thepressure inside the furnace was kept at 13.3 Pa (0.1 ton) to 1333 Pa (10ton), and the H₂/O₂ flow rate ratio was varied. Furthermore, it wasjudged that selective oxidation could be achieved in cases in whichtungsten was not oxidized but silicon was oxidized, and it was judgedthat selective oxidation could not be achieved in cases in which bothsilicon and tungsten were oxidized. In FIG. 8, O indicates thatselective oxidation could be achieved, and x indicates that selectiveoxidation could not be achieved. Also, Δ indicates that neither siliconnor tungsten was oxidized. Furthermore, the processing time was set at20 to 30 minutes.

It is seen from FIG. 8 that selective oxidation cannot be achieved incases in which the H₂/O₂ flow rate ratio is set at 1. When changes inthe surface of the tungsten were observed with an SEM in this case,needle-form crystals referred to as whiskers were observed (abnormaloxidation). It is seen that selective oxidation is possible in cases inwhich the H₂/O₂ flow rate ratio is set at 2 to 5. In this case, siliconwas sufficiently oxidized, and no abnormal oxidation of tungsten wasobserved. In cases in which the H₂/O₂ flow rate ratio was set at 10,tungsten was not oxidized, and silicon likewise showed hardly anyoxidation. It is thought that the cause of this was that the amount ofoxygen added was too small, and the oxidation rate was extremely low,indicating that this was not a practical level. It is seen from thesefindings that if the H₂/O₂ flow rate ratio is set in the range of 2 to5, silicon alone can be selectively oxidized without oxidizing tungsten,and that the silicon oxidation rate can be maintained at a practicallevel.

(2) Damage Recovery

Furthermore, in the present embodiment, as a result of the addition ofan extremely small amount of O₂ in a reducing atmosphere of H₂, it ispossible to recover from damage caused by the dry etching on a surfaceof the silicon substrate 100 and the surface layers of the side surfacesof the SiO₂ film 110, which is a thermal oxidation film, as well as ofthe poly-Si film 120, the insulating film 130 having an ONO structure,and the poly-Si film 140. Moreover, in order to recover from damagecaused by dry etching, it is preferable that the temperature at the timeof the introduction of O₂ be set at 800° C. or greater.

(3) Suppression of Oxidation in the Horizontal Direction

While the rate-determining step of conventional oxidation caused bymoisture (wet oxidation) is diffusion, in the case of oxidation causedby reaction species generated by the reaction of oxygen and hydrogen inthe present embodiment, there is no diffusion, and the reaction is closeto a surface reaction; accordingly, oxidation in the horizontaldirection is suppressed. In wet oxidation, the oxidizing species aresmall molecules of H₂O, and these diffuse through the oxidation film.For example, in a polymetal structure, as is shown in FIG. 5, not onlyis there oxidation of the surfaces (side surfaces) of the poly-Si films120, 140 and the like, but there is also, for example, oxidation thatproceeds in the horizontal direction (indicated by the arrow 51) alongthe lower part of the poly-Si film 120 as a result of the diffusion ofH₂O into the interface between the poly-Si film 120 and the SiO₂ film110, which is a gate oxidation film. The diffusion of H₂O is determinedby temperature and time. When the processing is performed for a longtime at a high temperature, diffusion is rapid, and oxidation in thehorizontal direction proceeds quickly. On the other hand, in the case ofthe reaction species in the present embodiment, since the lifetime isshort, the system returns to a steady state during diffusion through thefilm, the reaction species are oxygen and the like, and the oxidizingpower is weak. Accordingly, the progression of oxidation in thehorizontal direction is suppressed. Consequently, in the case of thereaction species in the present embodiment, oxidation is a reaction thatoccurs only in the surface layers (side surface layers).

(4) Stabilization of Interface State Between Silicon Substrate and SiO₂

An H₂ sintering effect is obtained by the advance introduction of H₂.For example, in a polymetal structure, as is shown in FIG. 5, a thingate oxidation film (in part, an oxide nitride film) is present in theinterface 52 between the silicon substrate 100 and the SiO₂ film 110.Ordinarily, in cases in which only an SiO₂ film 110 is formed, atransition region containing numerous unbonded species is present in theinterface between the SiO₂ film 110 and the silicon substrate 100, andthis transition region acts as an electron capturing center;accordingly, this has an effect on various characteristics, beginningwith the threshold voltage. Ordinarily, after the metal wiring step iscompleted, modification of the interface 52 between the SiO₂ film 110and silicon substrate 100 is also performed by H₂ annealing referred toas H₂ sintering processing, which is performed in order to embed varioustypes of defects. An effect similar to that of H₂ sintering is generatedby introducing hydrogen in advance, and by performing oxidation underhydrogen-rich conditions. Furthermore, since this is a process performedin the immediate vicinity of the gate, the efficiency of hydrogentermination is also improved. Accordingly, the state of the interface 52between a surface of the silicon substrate 100 and the SiO₂ film 110 canbe stabilized.

(5) Thin Film Formation at High Temperatures

In oxidation under hydrogen-rich conditions, the oxidation rate is lowerthan in the case of oxidation under oxygen-rich conditions.Conventionally, therefore, thin film formation at high temperatures hasbeen possible. As the processing temperature increases, stress in thefilm is relaxed, so that a high withstand voltage is obtained. Thereason for the slowing of the oxidation rate is the same as that in thecase of the selectivity described in (C)(1) above. As a result of thehydrogen-rich conditions, there are fewer oxidation reactions and moresublimation reactions. Furthermore, as the hydrogen-rich conditionsbecome more prevalent, oxidation no longer proceeds, and a state inwhich sublimation proceeds is entered via an equilibrium state.Accordingly, at the same oxidation temperature and pressure, theoxidation rate Becomes lower in the case of hydrogen-rich conditions,and oxidation films with a smaller thickness can be manufactured athigher temperatures while the film quality is improved. Furthermore, theadhesion of contaminants to a surface of the substrate can be reduced,and the substrate surface can easily be maintained in a clean state. Inaddition, when a plurality of silicon wafers 1 are processed using avertical semiconductor manufacturing apparatus, the variation in thethickness of the oxidation film that accompanies the variation in thehydrogen concentration on the respective silicon wafers 1 can besuppressed.

(6) Rounding Oxidation (Corner Rounding)

A rounding effect designed to reduce the concentration of the electricfield can be expected to be achieved by the reaction species in thepresent embodiment. For example, when a silicon surface having cornersis oxidized, a rearrangement of the atoms occurs; here, it is inferredthat the surface free energy is temporarily increased by the high-energyreaction species in the present embodiment, and that fluid motion of thesurface silicon takes place. When the surface energy is boosted by theenergy from the outside and causes rearrangement to take place, thisrearrangement moves to the form that is lowest in terms of energy. Theshape having the lowest surface energy is a spherical shape. Inaccordance with this reasoning, it is inferred that rounding oxidationis possible in principle as a result of the fact that rearrangementaccompanied by fluid motion of the silicon in the surface occurs at thesame time as oxidation is caused by the reaction species in the presentembodiment. For example, as is shown in FIG. 5, a shape with a rounding53 designed to reduce the concentration of the electric field may beexpected to be obtained in the boundary end between the poly-Si film 120and the SiO₂ film 110.

(D) Furthermore, in the present embodiment, since the introduction ofoxygen gas is stopped in the state in which the introduction of hydrogengas is continued, the oxidation of layers that contain metal atomsfollowing oxidation can be prevented. Furthermore, since theintroduction of hydrogen gas is continued from a point prior to the stepof increasing the temperature inside the processing chamber 4 to a pointfollowing the step of lowering the temperature inside the processingchamber, and the introduction of oxygen gas is performed at least duringthe step in which the temperature inside the processing chamber 4 ismaintained at the processing temperature, the oxidation of layers thatcontain metal atoms can be prevented from a point prior to theinitiation of temperature increase to a point following the completionof the lowering of the temperature.

(E) Furthermore, in the present embodiment, differences in the growthrates of oxidation films on silicon surfaces having different planeorientations (crystal plane orientations) on silicon substrates formedby various semiconductor wafer processing steps can be conspicuouslyreduced compared to conventional oxidation methods, and the planeorientation dependency of the oxidation rate can be reduced. Moreover,oxidation films can also be grown on Si₃N₄ films in the same manner ason silicon. Specifically, in addition to selective oxidation betweensilicon substrates and metal materials, isotropic oxidation can also beperformed between different silicon crystal orientations, and betweenSi₃N₄ films and silicon substrates.

FIG. 2 shows a comparative diagram of film thickness data for oxidationfilms formed on a surface of a silicon substrate using the oxidationprocessing method of the present embodiment and the oxidation processingmethod of a comparative example. Here, the film thicknesses of oxidationfilms formed on the surfaces of silicon substrates having differentcrystal plane orientations of (110) and (100) are also compared. Theoxidation conditions of the present embodiment were set as hydrogen-richconditions with hydrogen being introduced in advance (H₂ flow rate/O₂flow rate=1.0 slm/0.2 slm). The oxidation condition in the comparativeexample were oxygen-rich conditions (H₂ flow rate/O₂ flow rate=0.4slm/1.0 slm) with oxygen being introduced in advance. In all cases, thetemperature inside the furnace was fixed at 850° C., the pressure insidethe furnace was fixed at 35 Pa, and the processing time was also fixed.

It is seen from the same figure that in the oxidation processing methodof the present embodiment, the film thickness of the oxidation film is23.82 angstroms in the case of a silicon substrate having a crystalplane orientation of (110), and 23.63 angstroms in the case of a siliconsubstrate having a crystal plane orientation of (100). On the otherhand, in the oxidation processing method of the comparative example, itis seen that the film thickness of the oxidation film is 83.52 angstromsin the case of a silicon substrate having a crystal plane orientation of(110), and 73.55 angstroms in the case of a silicon substrate having acrystal plane orientation of (100), thus indicating that the oxidationprocessing method of present embodiment allows the formation of thinnerfilms than the oxidation processing method of the comparative example.Furthermore, in a case in which the oxidation processing method of thepresent embodiment and the oxidation processing method of thecomparative example were both performed with the pressure inside thefurnace set at normal pressure and the other oxidation conditions set inthe same manner as the oxidation conditions described above, the sameamount of H₂O gas was formed as in the case of 0.4 slm. It may be saidfrom these findings that the oxidation rate can be slowed under H₂-richconditions even at the same moisture content and with the temperatureand pressure set at the same values. Furthermore, in the oxidationprocessing method of the present embodiment, it is also seen from thefact that there is almost no difference in the film thickness of theoxidation film between a silicon substrate having a crystal planeorientation of (110) and a silicon substrate having a crystal planeorientation of (100) (difference in film thickness: 0.19 angstroms) thatthere is no plane orientation dependency, and that isotropy ismaintained (isotropy of (110)/(100)=1.01). In the oxidation processingmethod of the comparative example, on the other hand, it is seen thatthere is a relatively large difference in the film thickness of theoxidation film between a silicon substrate having a crystal planeorientation of (110) and a silicon substrate having a crystal planeorientation of (100) (difference in film thickness: 10 angstroms), thusindicating that there is plane orientation dependency, and that isotropyis not maintained (isotropy of (110)/(100)=1.14).

Furthermore, when a tungsten thin film was processed under thehydrogen-rich conditions with advance introduction of hydrogen in thepresent embodiment, and the sheet resistance before and after processingwas checked, the resistance before processing was 6.3Ω/□ (ohm/square),and the resistance after processing was 4.5Ω/□ (ohm/square), so that noincrease was seen, thus confirming that the oxidation of tungsten hadnot progressed. On the other hand, when a tungsten thin film wasprocessed under oxygen-rich conditions with the advance introduction ofoxygen in the comparative example, and the sheet resistance was checkedbefore and after processing, an increase was seen after processing, thusconfirming that the oxidation of tungsten had progressed.

Thus, in the present embodiment, differences in the growth rates ofoxidation films on silicon surfaces having different plane orientationson silicon substrates formed by various silicon substrate processingsteps can be conspicuously reduced compared to conventional oxidationmethods, and thinner films can be formed. Furthermore, as a result ofthe advance introduction of hydrogen, the oxidation of silicide filmsand metal thin films can be prevented, the initial-stage oxidation ofthe silicon substrate And the surfaces of polycrystalline silicon filmscan be prevented, and natural oxidation films can be removed. Moreover,by setting the conditions as hydrogen-rich conditions in which thehydrogen/oxygen flow rate ratio is 2.0 or greater when oxygen isintroduced while the introduction of hydrogen is continued, it ispossible to selectively form a thermal oxidation film that protects thesilicon substrate And surface of the polycrystalline film whilepreventing the oxidation of silicide films and metal thin films.

Furthermore, in the embodiment described above, a case was described inwhich oxygen (O₂) gas was used as an oxygen-containing gas. However, atleast one gas selected from the group including oxygen (O₂) gas, nitrousoxide (N₂O) gas, and nitrogen monoxide (NO) gas may be used.Furthermore, a case was described in which hydrogen (H₂) gas was used asa hydrogen-containing gas. However, at least one gas selected from thegroup including hydrogen (H₂) gas, deuterium (heavy hydrogen) gas,ammonia (NH₃) gas, and methane (CH₄) gas may be used.

Furthermore, for example, the layer that contains silicon atoms but doesnot contain metal atoms that is exposed at a surface of the substratemay be at least one layer selected from the group including a siliconsingle crystal substrate, a polycrystalline silicon film (poly-Si film)formed by CVD, a silicon nitride film (Si₃N₄ film), a silicon dioxidefilm (SiO₂ film), and an SiO₂/Si₃N₄/SiO₂ film (insulating film having anONO structure). Cases are also included in which a plurality of siliconlayers having different crystal plane orientations are formed on thesilicon single crystal substrate. In particular, the present inventionis especially effective in cases in which the surface of the siliconsubstrate that is subjected to oxidation processing has differentcrystal orientation planes, or has polycrystalline silicon formed byCVD, or has a silicon nitride.

Furthermore, the layer that contains metal atoms that is exposed at thesurface of the substrate may, for instance, be at least one layerselected from the group including silicide films, metal films, and metaloxide films. Here, such silicide films constitute at least one filmselected from the group including tungsten silicide (WSi) films,aluminum silicide (AlSi) films, nickel silicide (NiSi) films, molybdenumsilicide (MoSi₂) films, cobalt silicide (CoSi₂) films, and titaniumsilicide (TiSi₂) films. For example, metal films constitute at least onefilm selected from the group including tungsten (W) films, aluminum (Al)films, nickel (Ni) films, ruthenium (Ru) films, and copper (Cu) films.Furthermore, for instance, a W/WN/poly-Si structure may be cited as oneexample of a polymetal structure (metal/barrier metal/poly-Si).Moreover, metal oxide films may be oxide films of these metals.

Preferable aspects of the present invention are described below.

A first aspect is a manufacturing method of a semiconductor devicecomprising the steps of loading a substrate into a processing chamber,supplying an oxygen-containing gas and a hydrogen-containing gas intothe processing chamber and subjecting a surface of the substrate tooxidation processing, and unloading the substrate from the processingchamber following the oxidation processing, wherein, in the oxidationprocessing step, the hydrogen-containing gas is introduced in advanceinto the processing chamber, with the pressure inside the processingchamber set at a pressure that is less than atmospheric pressure, andthe oxygen-containing gas is then introduced in the state in which theintroduction of the hydrogen-containing gas is continued.

In this aspect, since a hydrogen-containing gas is introduced inadvance, early-stage oxidation of the substrate surface prior to[regular] oxidation can be suppressed, and natural oxidation films canbe removed.

A second aspect is the manufacturing method of a semiconductor device ofthe first aspect, the oxidation processing step comprising the steps of:increasing the temperature inside the processing chamber to a processingtemperature from the temperature at the time at which the substrate isloaded, maintaining the temperature inside the processing chamber at theprocessing temperature, and lowering the temperature inside theprocessing chamber from the processing temperature to the temperature atthe time at which the substrate is unloaded, wherein the introduction ofa hydrogen-containing gas is performed at least from the step ofincreasing the temperature inside the processing chamber, and theintroduction of an oxygen-containing gas is performed at least duringthe step of maintaining the temperature inside the processing chamber atthe processing temperature.

In this aspect, since the introduction of a hydrogen-containing gas isperformed at least from the step of increasing the temperature insidethe processing chamber, and the introduction of an oxygen-containing gasis performed at least during the step of maintaining the temperatureinside the processing chamber at the processing temperature, early-stageoxidation of the substrate surface during temperature increase can besuppressed, and natural oxidation films can be removed.

A third aspect is the manufacturing method of a semiconductor device ofthe first aspect, the oxidation processing step comprising the steps of:increasing the temperature inside the processing chamber to a processingtemperature from the temperature at the time at which the substrate isloaded, maintaining the temperature inside the processing chamber at theprocessing temperature, and lowering the temperature inside theprocessing chamber from the processing temperature to the temperature atthe time at which the substrate is unloaded, wherein the introduction ofa hydrogen-containing gas is performed from a point prior to the step ofincreasing the temperature inside the processing chamber, and theintroduction of an oxygen-containing gas is performed at least duringthe step of maintaining the temperature inside the processing chamber atthe processing temperature.

In this aspect, since the introduction of a hydrogen-containing gas isperformed from a point prior to the step of increasing the temperatureinside the processing chamber, and the introduction of anoxygen-containing gas is performed at least during the step ofmaintaining the temperature inside the processing chamber at theprocessing temperature, early-stage oxidation of the substrate surfacefrom a point prior to temperature increase can be suppressed, andnatural oxidation films can be removed.

A fourth aspect is the manufacturing method of a semiconductor device ofthe first aspect, wherein the pressure inside the processing chamber atthe time that a hydrogen-containing gas is introduced in advance in theoxidation processing step is set at a greater pressure than the pressureat the time that an oxygen-containing gas is introduced in the state inwhich the introduction of a hydrogen-containing gas is continued.

In this aspect, since the pressure inside the processing chamber at thetime that a hydrogen-containing gas is introduced in advance in theoxidation processing step is set at a greater pressure than the pressureat the time that an oxygen-containing gas is introduced in the state inwhich the introduction of a hydrogen-containing gas is continued,roughness of the substrate surface caused by thermal etching can beprevented.

A fifth aspect is the manufacturing method of a semiconductor device ofthe first aspect, wherein at least a layer that contains silicon atomsbut does not contain metal atoms, and a layer that contains metal atomsare exposed at a surface of the substrate.

In this aspect, in cases in which at least a layer that contains siliconatoms but does not contain metal atoms, and a layer that contains metalatoms are exposed at the surface of the substrate, early-stage oxidationof the layer that contains silicon atoms but does not contain metalatoms prior to [regular] oxidation can be suppressed, natural oxidationfilms can be removed, and oxidation of the layer that contains metalatoms can be prevented.

A sixth aspect is the manufacturing method of a semiconductor device ofthe fifth aspect, wherein the flow rate ratio B/A of the flow rate B ofthe hydrogen-containing gas to the flow rate A of the oxygen-containinggas in the oxidation processing step is set at 2 or greater.

In this aspect, since the flow rate ratio B/A of the flow rate B of thehydrogen-containing gas to the flow rate A of the oxygen-containing gasis set at 2 or greater, an oxidation film for protecting the layer thatcontains silicon atoms but does not contain metal atoms can beselectively formed while preventing the oxidation of the layer thatcontains metal atoms. Furthermore, it is possible to recover from damageto the surface layer received in the steps prior to the oxidationprocessing step. Moreover, oxidation in the horizontal directionperpendicular to the direction of thickness of the layer that containssilicon atoms but does not contain metal atoms can be suppressed.Furthermore, the interface state between the substrate surface and thelayer that contains silicon atoms but does not contain metal atoms canbe stabilized. In addition, thin films can be manufactured at a highertemperature while improving the film quality. Furthermore, in cases inwhich the layer that contains silicon atoms but does not contain metalatoms has ends where the electric field tends to be concentrated,rounding designed to reduce the concentration of the electric field canbe formed on these ends.

A seventh aspect is the manufacturing method of a semiconductor deviceof the sixth aspect, wherein the pressure inside the processing chamberat the time that an oxygen-containing gas is introduced in the state inwhich the introduction of a hydrogen-containing gas is continued in theoxidation processing step is set at 1333 Pa (10 ton) or less.

In this aspect, since the pressure inside the processing chamber at thetime that an oxygen-containing gas is introduced in the state in whichthe introduction of a hydrogen-containing gas is continued is set at1333 Pa (10 torr) or less, the probability of a reaction between oxygenand hydrogen is lowered, and the explosive range can be avoided;furthermore, isotropic oxidation is possible.

An eighth aspect is the manufacturing method of a semiconductor deviceof the fifth aspect, wherein a hydrogen-containing gas is introduced inadvance into the processing chamber in the oxidation processing step, anoxygen-containing gas is then introduced in the state in which theintroduction of a hydrogen-containing gas is continued, and theintroduction of an oxygen-containing gas is subsequently stopped in thestate in which the introduction of a hydrogen-containing gas iscontinued.

In this aspect, since the introduction of an oxygen-containing gas isstopped in the state in which the introduction of a hydrogen-containinggas is continued, oxidation of the layer that contains metal atomsfollowing [regular] oxidation can be prevented.

A ninth aspect is the manufacturing method of a semiconductor device ofthe fifth aspect, the oxidation processing step comprising the steps of:increasing the temperature inside the processing chamber to a processingtemperature from the temperature at the time at which the substrate isloaded, maintaining the temperature inside the processing chamber at theprocessing temperature, and lowering the temperature inside theprocessing chamber from the processing temperature to the temperature atthe time at which the substrate is unloaded, wherein the introduction ofa hydrogen-containing gas is continued from at least the step ofincreasing the temperature inside the processing chamber to the point atwhich the step of lowering of the temperature inside the processingchamber is completed, and the introduction of an oxygen-containing gasis performed at least during the step of maintaining the temperatureinside the processing chamber at the processing temperature.

In this aspect, since the introduction of a hydrogen-containing gas iscontinued from at least the step of increasing the temperature insidethe processing chamber to the point at which the step of lowering of thetemperature; inside the processing chamber is completed, and theintroduction of an oxygen-containing gas is performed at least duringthe step of maintaining the temperature inside the processing chamber atthe processing temperature, oxidation of the layer that contains metalatoms can be prevented from the time that temperature increase isinitiated to the time that lowering of the temperature is completed.

A tenth aspect is the manufacturing method of a semiconductor device ofthe fifth aspect, the oxidation processing step comprising the steps of:increasing the temperature inside the processing chamber to a processingtemperature from the temperature at the time at which the substrate isloaded, maintaining the temperature inside the processing chamber at theprocessing temperature, and lowering the temperature inside theprocessing chamber from the processing temperature to the temperature atthe time at which the substrate is unloaded, wherein the introduction ofa hydrogen-containing gas is continued from a point prior to the step ofincreasing the temperature inside the processing chamber to a pointfollowing the step of lowering the temperature inside the processingchamber, and the introduction of an oxygen-containing gas is performedat least during the step of maintaining the temperature inside theprocessing chamber at the processing temperature.

In this aspect, since the introduction of a hydrogen-containing gas iscontinued from a point prior to the step of increasing the temperatureinside the processing chamber to a point following the step of loweringthe temperature inside the processing chamber, and the introduction ofan oxygen-containing gas is performed at least during the step ofmaintaining the temperature inside the processing chamber at theprocessing temperature, oxidation of the layer that contains metal atomscan be prevented from a point prior to the time that temperatureincrease is initiated to a point after the time that lowering of thetemperature is completed

An eleventh aspect is the manufacturing method of a semiconductor deviceof the fifth aspect, wherein the layer that contains silicon atoms butdoes not contain metal atoms is at least one layer selected from thegroup including a silicon single crystal substrate, polycrystallinesilicon film (poly-Si film), silicon nitride film (Si₃N₄ film), andsilicon dioxide film (SiO₂ film), and the layer that contains metalatoms is at least one layer selected from the group including a silicidefilm, a metal film, and a metal oxide film.

In cases in which the oxidation processing of a substrate having suchlayers is performed, the following problems arise: namely, the layerthat contains silicon atoms but does not contain metal atoms isespecially susceptible to early-stage oxidation prior to [the regular]oxidation, and the layer that contains metal atoms is susceptible tooxidation. In the present aspect, however, such problems are solved.

A twelfth aspect is a manufacturing method of a semiconductor devicecomprising the steps of loaded into a processing chamber a substrate inwhich at least a layer that contains silicon atoms but does not containmetal atoms and a layer that contains metal atoms are exposed at thesurface, supplying an oxygen-containing gas and a hydrogen-containinggas into the processing chamber and subjecting a surface of thesubstrate to oxidation processing, and loading the substrate subjectedto oxidation processing from the processing chamber, wherein, in theoxidation processing step, the pressure inside the processing chamber isset at a pressure that is less than atmospheric pressure, and the flowrate ratio B/A of the flow rate B of the hydrogen-containing gas to theflow rate A of the oxygen-containing gas is set at 2 or greater.

In this aspect, since a substrate in which at least a layer thatcontains silicon atoms but does not contain metal atoms and a layer thatcontains metal atoms are exposed at the surface is subjected tooxidation processing by supplying an oxygen-containing gas and ahydrogen-containing gas whose flow rate ratio B/A is set at 2 orgreater, an oxidation film for protecting the layer that containssilicon atoms but does not contain metal atoms can be selectively formedwhile preventing the oxidation of the layer that contains metal atoms.Furthermore, it is also possible to recover from damage to the surfacelayers that is received in the steps preceding the oxidation processingstep. Moreover, oxidation in the horizontal direction perpendicular tothe direction of thickness of the layer that contains silicon atoms butdoes not contain metal atoms can be suppressed. Furthermore, theinterface state between the surface of the substrate And the layer thatcontains silicon atoms but does not contain metal atoms can bestabilized. In addition, thin films can be formed at higher temperatureswhile improving the film quality. Furthermore, in cases in which thelayer that contains silicon atoms but does not contain metal atoms hasends where the electric field tends to be concentrated, roundingdesigned to reduce the concentration of the electric field can be formedon these ends.

A thirteenth aspect is the manufacturing method of a semiconductordevice of the twelfth aspect, wherein the pressure inside the processingchamber and the flow rate ratio B/A are set in the oxidation processingstep in a range in which only the layer that contains silicon atoms butdoes not contain metal atoms is selectively oxidized without anyoxidation of the layer that contains metal atoms.

In this aspect, since the pressure inside the processing chamber and theflow rate ratio B/A are set in a range in which only the layer thatcontains silicon atoms but does not contain metal atoms is selectivelyoxidized without any oxidation of the layer that contains metal atoms,only the layer that contains silicon atoms but does not contain metalatoms can be selectively oxidized without any oxidation of the layerthat contains metal atoms.

A fourteenth aspect is the manufacturing method of a semiconductordevice of the twelfth aspect, wherein, in the oxidation processing step,the pressure inside the processing chamber is set at 1333 Pa (10 ton) orless, and the flow rate ratio B/A is set at 2 or greater.

In this aspect, since the pressure inside the processing chamber is setat 1333 Pa (10 ton) or less, and the flow rate ratio B/A is set at 2 orgreater, only the layer that contains silicon atoms but does not containmetal atoms can be selectively oxidized without any oxidation of thelayer that contains metal atoms.

A fifteenth aspect is the manufacturing method of a semiconductor deviceof the twelfth aspect, wherein the pressure inside the processingchamber is set at 1333 Pa (10 ton) or less, and the flow rate ratio B/Ais set at a value ranging from 2 or greater to 5 or less.

In this aspect, since the pressure inside the processing chamber is setat 1333 Pa (10 torr) or less, and the flow rate ratio B/A is set at avalue ranging from 2 or greater to 5 or less, only the layer thatcontains silicon atoms but does not contain metal atoms can beselectively oxidized without any oxidation of the layer that containsmetal atoms, and the oxidation rate can be kept within a practicalrange.

A sixteenth aspect is a substrate processing apparatus comprising aprocessing chamber in which a substrate is processed, anoxygen-containing gas supply line which supplies an oxygen-containinggas into the processing chamber, a hydrogen-containing gas supply linewhich supplies a hydrogen-containing gas into the processing chamber, anexhaust line which evacuates the interior of the processing chamber, avacuum pump which is connected to the exhaust line and which evacuatesthe interior of the processing chamber to a vacuum, and a controllerwhich performs a control action so that the pressure inside theprocessing chamber is set at a pressure that is less than atmosphericpressure, the hydrogen-containing gas is introduced in advance into theprocessing chamber, and the oxygen-containing gas is then introduced inthe state in which the introduction of the hydrogen-containing gas iscontinued.

In this aspect, since control is performed using a controller so that ahydrogen-containing gas is introduced in advance, early-stage oxidationof the substrate surface prior to [the regular] oxidation can easily besuppressed, and natural oxidation films can easily be removed.

A seventeenth aspect is a substrate processing apparatus comprising aprocessing chamber for processing a substrate in which at least a layerthat contains silicon atoms but does not contain metal atoms and a layerthat contains metal atoms are exposed at the surface, anoxygen-containing gas supply line which supplies an oxygen-containinggas into the processing chamber, a hydrogen-containing gas supply linewhich supplies a hydrogen-containing gas into the processing chamber, anexhaust line which evacuates the interior of the processing chamber, avacuum pump which is connected to the exhaust line and which evacuatesthe interior of the processing chamber to a vacuum, and a controllerwhich performs a control action so that the pressure inside theprocessing chamber is set at a pressure that is less than atmosphericpressure, and so that the flow rate ratio B/A of the flow rate B of thehydrogen-containing gas to the flow rate A of the oxygen-containing gassupplied to the processing chamber is set at 2 or greater.

In this aspect, since control is performed using a controller so that asubstrate in which at least a layer that contains silicon atoms but doesnot contain metal atoms and a layer that contains metal atoms areexposed at the surface is subjected to oxidation processing underhydrogen-rich processing in which the flow rate ratio B/A is set at 2 orgreater, an oxidation film for protecting the layer that containssilicon atoms but does not contain metal atoms can be selectively formedwith ease while easily preventing oxidation of the layer that containsmetal atoms. Furthermore, it is possible to recover from damage to thesurface layer received in steps preceding the oxidation processing step.Moreover, oxidation in the horizontal direction perpendicular to thedirection of thickness of the layer that contains silicon atoms but doesnot contain metal atoms can easily be suppressed. In addition, theinterface state between the substrate surface and the layer thatcontains silicon atoms but does not contain metal atoms can easily bestabilized. Furthermore, thin films can easily be formed at highertemperatures while improving the film quality. Moreover, in cases inwhich the layer that contains silicon atoms but does not contain metalatoms has ends in which the electric field tends to be concentrated,rounding designed to reduce the concentration of the electric field caneasily be formed on these ends.

1. A substrate processing apparatus comprising: a processing chamber inwhich a substrate is processed; an oxygen-containing gas supply linewhich supplies an oxygen-containing gas into said processing chamber; ahydrogen-containing gas supply line which supplies a hydrogen-containinggas into said processing chamber; an exhaust line which evacuates theinterior of said processing chamber; a vacuum pump which is connected tosaid exhaust line and which evacuates the interior of said processingchamber to a vacuum; and a controller which performs a control action sothat in a state in which said substrate is loaded into said processingchamber, a pressure inside said processing chamber is set at a pressurethat is less than atmospheric pressure, the hydrogen-containing gas isintroduced in advance into said processing chamber, theoxygen-containing gas is then introduced in a state in which theintroduction of the hydrogen-containing gas is continued and a surfaceof said substrate is thereby subjected to oxidation processing.
 2. Asubstrate processing apparatus comprising: a processing chamber in whicha substrate is processed; an oxygen-containing gas supply line whichsupplies an oxygen-containing gas into said processing chamber; ahydrogen-containing gas supply line which supplies a hydrogen-containinggas into said processing chamber; an exhaust line which evacuates theinterior of said processing chamber; a vacuum pump which is connected tosaid exhaust line and which evacuates the interior of said processingchamber to a vacuum; and a controller which performs a control action sothat in a state in which a substrate, in which at least a layer thatcontains silicon atoms but does not contain metal atoms and a layer thatcontains metal atoms are exposed at the surface, is loaded into theprocessing chamber, a pressure inside said processing chamber is set ata pressure that is less than atmospheric pressure, a flow rate ratio B/Aof a flow rate B of the hydrogen-containing gas to a flow rate A of theoxygen-containing gas supplied into said processing chamber is set at 2or greater, and a surface of said substrate is thereby subjected tooxidation processing.
 3. The substrate processing apparatus according toclaim 1, wherein said controller is further configured to perform thecontrol action so that a temperature inside said processing chamber isincreased to a processing temperature from a temperature at the time atwhich said substrate is loaded into said processing chamber, thetemperature inside said processing chamber is maintained at saidprocessing temperature, the temperature inside said processing chamberis lowered from said processing temperature to a temperature at the timeat which said substrate is unloaded from said processing chamber, theintroduction of said hydrogen-containing gas is performed at least fromthe time at which the temperature inside said processing chamber isincreased, and the introduction of said oxygen-containing gas isperformed at least during the period in which the temperature insidesaid processing chamber is maintained at said processing temperature. 4.The substrate processing apparatus according to claim 1, wherein saidcontroller is further configured to perform the control action so that atemperature inside said processing chamber is increased to a processingtemperature from a temperature at the time at which said substrate isloaded into said processing chamber, the temperature inside saidprocessing chamber is maintained at said processing temperature, thetemperature inside said processing chamber is lowered from saidprocessing temperature to a temperature at the time at which saidsubstrate is unloaded from said processing chamber, the introduction ofsaid hydrogen-containing gas is performed from a point prior to the timeat which the temperature inside said processing chamber is increased,and the introduction of said oxygen-containing gas is performed at leastduring the period in which the temperature inside said processingchamber is maintained at said processing temperature.
 5. The substrateprocessing apparatus according to claim 1, wherein said controller isfurther configured to perform the control action so that the pressureinside said processing chamber at the time at which saidhydrogen-containing gas is introduced in advance is set at a value thatis greater than the pressure inside said processing chamber at the timeat which said oxygen-containing gas is introduced in a state in whichthe introduction of said hydrogen-containing gas is continued.
 6. Thesubstrate processing apparatus according to claim 1, wherein at least alayer that contains silicon atoms but does not contain metal atoms and alayer that contains metal atoms are exposed at the surface of saidsubstrate subjected to oxidation processing.
 7. The substrate processingapparatus according to claim 6, wherein said controller is furtherconfigured to perform the control action so that a flow rate ratio B/Aof a flow rate B of said hydrogen-containing gas to a flow rate A ofsaid oxygen-containing gas is set at 2 or greater.
 8. The substrateprocessing apparatus according to claim 7, wherein said controller isfurther configured to perform the control action so that the pressureinside said processing chamber at the time at which saidoxygen-containing gas is introduced in a state in which the introductionof said hydrogen-containing gas is continued is set at 1333 Pa or less.9. The substrate processing apparatus according to claim 6, wherein saidcontroller is further configured to perform the control action so thatsaid hydrogen-containing gas is introduced in advance into saidprocessing chamber, said oxygen-containing gas is then introduced in astate in which the introduction of said hydrogen-containing gas iscontinued, and the introduction of said oxygen-containing gas issubsequently stopped in the state in which the introduction of saidhydrogen-containing gas is continued.
 10. The substrate processingapparatus according to claim 6, said controller is further configured toperform the control action so that a temperature inside said processingchamber is increased to a processing temperature from a temperature atthe time at which said substrate is loaded into said processing chamber,the temperature inside said processing chamber is maintained at saidprocessing temperature, the temperature inside said processing chamberis lowered from said processing temperature to a temperature at the timeat which said substrate is unloaded from said processing chamber, theintroduction of said hydrogen-containing gas is continued at least fromthe time at which the temperature inside said processing chamber isincreased to the time at which the lowering of the temperature insidesaid processing chamber is completed, and the introduction of saidoxygen-containing gas is performed at least during the period in whichthe temperature inside said processing chamber is maintained at saidprocessing temperature.
 11. The substrate processing apparatus accordingto claim 6, wherein said controller is further configured to perform thecontrol action so that a temperature inside said processing chamber isincreased to a processing temperature from a temperature at the time atwhich said substrate is loaded into said processing chamber, thetemperature inside said processing chamber is maintained at saidprocessing temperature, the temperature inside said processing chamberis lowered from said processing temperature to a temperature at the timeat which said substrate is unloaded from said processing chamber, theintroduction of said hydrogen-containing gas is continued from a pointprior to the time at which the temperature inside said processingchamber is increased to a point following the time at which the loweringof the temperature inside said processing chamber is completed, and theintroduction of said oxygen-containing gas is performed at least duringthe period in which the temperature inside said processing chamber ismaintained at said processing temperature.
 12. The substrate processingapparatus according to claim 6, wherein said layer that contains siliconatoms but does not contain metal atoms is at least one layer selectedfrom the group including a silicon single crystal substrate, apolycrystalline silicon film, a silicon nitride film, and a silicondioxide film, and said layer that contains metal atoms is at least onelayer selected from the group including a silicide film, a metal film,and a metal oxide film.
 13. The substrate processing apparatus accordingto claim 2, wherein said controller is further configured to perform thecontrol action so that the pressure inside said processing chamber andsaid flow rate ratio B/A are set in a range in which only said layerthat contains silicon atoms but does not contain metal atoms isselectively oxidized without any oxidation of said layer that containsmetal atoms.
 14. The substrate processing apparatus according to claim2, wherein, said controller is further configured to perform the controlaction so that the pressure inside said processing chamber is set at1333 Pa or less, and said flow rate ratio B/A is set at 2 or greater.15. The substrate processing apparatus according to claim 2, wherein,said controller is configured to perform the control action so that thepressure inside said processing chamber is set at 1333 Pa or less, andsaid flow rate ratio B/A is set at a value ranging from 2 or greater to5 or less.